Azopyridone compounds, compositions and use

ABSTRACT

Compositions containing a solvent and at least one compound of Formula (1)                    
     in which: 
     R 1  represents H, an optionally substituted C 1-8 carbyl derived group, or a group of Formula A:                    
     in which c is from 2 to 6; R 3  represents H or optionally substituted C 1-8 carbyl derived group; R 4  and R 5  independently represent an optional substituent; R 2  represents an optionally substituted C 1-8 carbyl derived group; X, Y and Z independently represent H or an optional substituent; M represents H or a cation; and m and n independently represent 0, 1 or 2, are useful as colorants for color filters for displays. Compounds of Formula (1) wherein at least one of R 1 , R 2 , X, Y or Z, represent SO 3 M or PO 3 M 2  are also provided.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a national phase application based onPCT/GB00/03550, filed Sep. 18, 2000, and which further claims priorityfrom British Application No. 9922136.8, filed Sep. 20, 1999. Theseapplications in their entirety are incorporated herein by reference.

This invention relates to compounds, compositions, patterned substrates(such as displays and colour filters) comprising these colorants and tomethods of making thesame.

The ability to produce brightly coloured patterns or images onsubstrates, where the colour has high resistance (fastness) to light,water, heat and/or solvents is important in many areas of for instancethe electronics and printing industries. Examples of this are in theproduction of colour filters, in ink-jet printing and inelectrophotographic imaging. Thus it is important to discover colorantswhich can be readily used (and/or formulated into inks for use) in suchapplications.

Colour filters, alternatively known as optical filters, are a componentof coloured liquid crystal displays (LCDs) used as flat screen displays,for example, in small television receivers or portable computers.

Dyes of the following formulae are known:

Dyes of structures II & III are water soluble monoazo pyridones used ascellulose reactive dyes as described in EP 169,457 B1 (Hoechst). The dyeof structure IV is described in GB 1,359,171 (Ciba-Geigy), as a dye forwool or cellulosics. The dye of structure I in which a pyridone moietyis bound to a zinc phthalocyanine is described in JP-A 01-303407 (NipponKayaku) as a one component green dye for colour filters. This isdifferent from the present invention in which a yellow dye is used as aseparate component of a green ink for colour filters. This offers muchgreater flexibility in adjusting the precise shade of the ink and alsois advantageous over zinc phthalocyanines which are less favoured due topoor light fastness.

Known mixtures of copper phthalocyanines and azopyridone yellow dyes(such as the dyes exemplified in JP2701387B2 [Mitsubishi Kasei Corp])are unsatisfactory for use in colour filter applications because of poorlight fastness. However, green colour filters containing azopyridoneyellow dyes are significantly brighter than those produced usingalternative yellow chromophores such as azobenzenes, azopyrazolones,metallised azo dyes and yellow pigments, which are prevalent in the art.

It is desirable therefore to find improved colorants for use in colourfilters, in particular colorants which can be used either alone forexample as a yellow or as a yellow component in a mixture (e.g. withcyan colorants such as phthalocyanines). It is a preferred object of apreferred aspect of the invention to discover a green colorantcomprising a mixture of one or more yellow colorants with one or morecyan colorants which is of particular use in a colour filter, optionallywith improved properties such as light fastness and/or brightness.

The present invention provides azopyridone compounds of use in preparingpatterned colored substrates such as colour filters. The compounds givestable inks with advantageous properties. As a preferred aspect of thepresent invention the applicant has surprisingly discovered certainsimple pyridone dyes containing carboxy groups ortho to the azo linkagehave a significant advantage in terms of light fastness versus relatedortho-sulpho analogues, with no loss in brightness.

According to the present invention there is provided a compositioncomprising a solvent and at least one compound of Formula (1)

in which:

R¹ represents H, an optionally substituted C₁₋₈carbyl derived group, ora group of Formula A:

where:

c is from 2 to 6;

R³ represents H or optionally substituted C₁₋₈carbyl derived group;

R⁴ and R⁵ independently represent an optional substituent;

R² represents an optionally substituted C₁₋₈carbyl derived group;

X, Y and Z independently represent H or an optional substituent group;

M represents H or a cation; and

m and n independently represent 0, 1 or 2.

The azopyridones of Formula (1) are particularly suitable for use incolour filters, giving very bright yellow films with good lightfastness, and as components of ink-jet inks. Conveniently compounds ofFormula (1) are not pyridinium pyridones (i.e. Z is not pyridinium).

Preferred compounds of Formula (1) are those in which:

R¹ represents H, optionally substituted alkyl, a group of Formula[R⁹O]_(a)R⁶, or a group of Formula A

R² represents alkyl, especially C₁₋₄alkyl more especially methyl, orCH₂SO₃M,

X and Y independently represent SO₃M, CO₂M, PO₃M₂, SO2NR⁶R⁷, CONR⁶R⁷,CO₂R⁶, COR⁶, alkyl, alkoxy, NR⁶COR⁷, halogen, NO₂, NR⁷R⁸;

where R⁶ and R⁷ independently represent H, optionally substitutedC₁₋₆alkyl, optionally substituted aryl; and R⁸ represents R⁶ or asubstituted triazinyl group;

Z represents CN, CONH₂, H or CH₂SO₃M;

R³ represents H or optionally substituted C₁₋₈carbyl derived group;

R⁴ and R⁵ independently represent halo, SO₃M, NR⁶R⁷, OR⁶ or SR⁷;

M represents H, alkali metal ion, ammonium, or a quatemary ammoniumcation (hereinafter QAC); more preferably M is Li⁺, Na⁺, K⁺ or NH₄ ⁺;

m, n is 0, 1 or 2;

a is an integer from 1 to 10, more preferably from 1 to 5, especially 2to 3;and each R⁹ is independently ethylene or propylene:

with the proviso that at least one of R¹ to R⁸, X, Y or Z comprises agroup of Formula SO₃M or PO₃M₂; and the compound of Formula (1) is otherthan a compound of Formula II, III or IV as described herein.

Preferred QAC's are those containing C₁₋₃₀ , alkyl chains. Morepreferred QAC cations may be selected from one or more of the following:N,N-diethyl-N-dodecyl-N-benzylammonium;N,N-dimethyl-N-octadecyl-N-(dimethylbenzyl) ammonium;N,N-dimethyl-N,N-didecyl ammonium; N,N-dimethyl-N,N-didodecyl ammonium;N,N,N-trimethyl-N-tetradecylammonium;N-benzyl-N,N-dimethyl-N-(C₁₂₋₁₈alkyl)ammonium;N-(dichlorobenzyl)-N,N-dimethyl-N-dodecylammonium; N-hexadecylpyridinium; N-hexa decyl-N,N,N-trimethylammonium, dodecylpyridinium;N-benzyl-N-dodecyl-N,N-bis(hydroxyethyl)ammonium;N-dodecyl-N-benzyl-N,N-dimethylammonium;N-benzyl-N,N-dimethyl-N-(C₁₂₋₁₈alkyl)ammonium;N-dodecyl-N,N-dimethyl-N-(1-naphthylmethyl) ammonium andN-hexadecyl-N,N-dimethyl-N-benzylammonium cations.

Suitable QAC cations may also be formed from suitable amines for examplefrom one or more amines selected from: isononylamine, dodecylamine,octadecylamine, didecylamine, didodecylamine, tetradecylamine,hexadecylamine, mixed C₁₂₋₁₈alkylamines and N-benzyl amines. Preferredamines which may be used to from suitable QAC comprise N-C₁₋₆alkylprimary amines, N,N-di-C₁₋₈alkyl secondary amines and N-benzyl amines.Particularly preferred amines comprise methyl and ethyl aminederivatives.

Preferably at least one of R¹, R², X, Y or Z comprises a group ofFormula SO₃M or PO₃M₂ where M is independently as represented herein;when n is 0; m is 1; X is a sulpho group para to the azo group; Z is Hand R² is methyl then R¹ is other than ethyl and the compound of Formula(1) is other than a compound of Formula II, III or IV as describedherein.

More preferred compounds of Formula (1) are of Formula (2):

in which

Z is CONH₂, CN or H;

R¹ is optionally substituted C₂₋₈alkyl (preferably hydroxy substituted)or a glycol group (for example CH₂CH₂OCH₂CH₃ or CH₂CH₂OCH₂CH₂OH);

with the proviso that if the SO₃M group is in the 4-position of thebenzene ring then either R¹ is other than ethyl or Z is other than H.

In general, preferred compounds of the invention are those which giveparticularly bright yellow films and prints, and are easily synthesisedfrom readily available intermediates. Solubility in an aqueous ink isalso desirable, hence compounds of Formula (1) comprise at least oneSO₃M or PO₃M₂ group, comprise substituent (e.g. R¹) of C₈ (or less)carbyl-derived groups. To improve solubility optionally R¹ comprises atleast one PEG and/or OH group.

Compounds of the present invention can be prepared by analogy to any ofthe methods known in the art, for example as in GB 1,271,226.

According to a further aspect of the present invention there is provideda compound of Formula (1) as hereinbefore defined with the provisosthat:

at least one of R¹, R², X, Y or Z comprises a group of Formula SO₃M orPO₃M₂ where M is independently as represented herein;

when n is 0; m is 1; X is a sulpho group para to the azo group; Z is Hand R² is methyl then R¹ is other than ethyl; and

the compound of Formula (1) is other than a compound of Formula II, IIIor IV as described herein.

Preferences for the substituents in Formula (1) are as hereinbeforedefined in relation to the composition. Especially preferred compoundsof the invention are of Formula (2) as hereinbefore defined.

Preferably the solvent comprises water or more preferably water and oneor more water soluble organic solvents.

The viscosity of the composition is preferably less than 100 cp, morepreferably less than 50 cp, especially less than 20 cp, more especiallyless than 15 cp and most preferably less than 10 cp at 20° C.

Preferably the composition has been filtered through a filter having amean pore size below 10 μm, preferably below 5 μm, more preferably below2 μm, especially below 0.5 μm. In this way particulate matter is removedwhich could otherwise block fine nozzles in an ink-jet printer.

The composition preferably has a total concentration of divalent andtrivalent metal ions, other than those bound to the pigment, below 5000,more preferably below 1000, especially below 100, more especially below20 parts per million by weight relative to the total weight of thecomposition. Pure compositions of this type may be prepared by usinghigh purity ingredients and/or by purifying the composition after it hasbeen prepared.

Suitable purification techniques are well known, for exampleultrafiltration, reverse osmosis, ion exchange and combinations thereof.

When in the formulae herein there is a list of labels (e.g. Ar¹ and Ar²)or indices (e.g. ‘n’) which are said to represent a list of groups ornumerical values, and these are said to be “independent in each case”this indicates each label and/or index can represent any of those groupslisted: independently from each other, independently within each repeatunit, independently within each Formula and/or independently on eachgroup which is substituted; as appropriate. Thus in each of theseinstances many different groups might be represented by a single label(e.g. Ar¹).

The term ‘halo’ as used herein signifies fluoro, chloro, bromo and iodo.

The terms ‘optional substituent’ and/or ‘optionally substituted’ as usedherein (unless followed by a list of other substituents) signifies theone or more of following groups (or substitution by these groups):carbyl, carboxy, sulpho, phospho, formyl, hydroxy, amino, imino,nitrilo, mercapto, cyano, nitro, halo and/or combinations thereof. Theseoptional groups include all chemically possible combinations in the samemoiety of a plurality (preferably two) of the aforementioned groups(e.g. amino and sulphonyl if directly attached to each other represent asulphamoyl radical).

The term carbyl as used herein denotes any monovalent or multivalentorganic radical moiety which comprises at least one carbon atom eithersolely (e.g. —C≡C—) or optionally combined with at least one othernon-carbon atom (e.g. alkyl, carbonyl etc.). The non-carbon atom(s) maycomprise any elements other than carbon (including any chemicallypossible mixtures or combinations thereof) that together with carbon cancomprise an organic radical moiety. Preferably the non-carbon atom isselected from at least one hydrogen and/or heteroatom, more preferablyfrom at least one: hydrogen, phosphorus, halo, nitrogen, oxygen and/orsulphur, most preferably from at least one hydrogen, nitrogen, oxygenand/or sulphur. Carbyl groups include all chemically possiblecombinations in the same group of a plurality (preferably two) of theaforementioned carbon and/or non-carbon atom containing moieties (e.g.alkoxy and carbonyl if directly attached to each other represent analkoxycarbonyl radical).

Preferably ‘carbyl-derived’ moieties comprise at least one of thefollowing carbon containing moieties: alkyl, alkoxy, alkanoyl, carboxy,carbonyl, formyl and/or combinations thereof; optionally in combinationwith at least one of the following heteroatom containing moieties: oxy,thio, sulphinyl, sulphonyl, amino, imino, nitrilo and/or combinationsthereof.

The term ‘hydrocarbyl’ as used herein (which is encompassed by the term‘carbyl-derived’) denotes any radical moiety which consists only of atleast one hydrogen atom and at least one carbon atom. A hydrocarbylgroup may however be optionally substituted.

More preferably ‘hydrocarbyl derived’ moieties comprise one or more ofthe following carbon containing moieties: alkyl, aryl, alkaryl and/orcombinations thereof. The term ‘aryl’ as used herein signifies a radicalwhich comprises an aromatic hydrocarbon ring, for example phenyl,naphthyl, anthryl and phenanthryl radicals. The term ‘alkyl’ or itsequivalent (e.g. ‘alk’) as used herein may be readily replaced, whereappropriate, by terms denoting a different degree of saturation and/orvalence e.g. moieties that comprise double bonds, triple bonds, and/oraromatic moieties (e.g. alkenyl, alkynyl and/or aryl) as well asmultivalent species attached to two or more substituents (such asalkylene).

Any radical group mentioned herein as a substituent refers to amonovalent radical unless otherwise stated. A group which comprises achain of three or more atoms signifies a group in which the chain may bestraight or branched or the chain or part of the chain may form a ring.For example, an alkyl group may comprise: propyl which includes n-propyland isopropyl; butyl which includes n-butyl, sec-butyl, isobutyl andtert-butyl; and an alkyl group of three or more carbon atoms maycomprise a cycloalkyl group. The total number of certain atoms isspecified herein for certain substituents, for example C_(1-n)alkyl,signifies an alkyl group having from 1 to n carbon atoms. Preferredalkyl groups in compounds of Formulae (1) and (2) may be branched orstraight chain and preferred branched chain alkyl groups are α-branchedalkyl groups.

Advantageously the optional substituents and/or carbyl derived groupswhich may be present in Formula (1) herein may be each independentlyselected from: carboxy, sulpho, phospho, nitro, bromo, chloro fluoro,alkyl (especially C₁₋₄alkyl) alkoxy (especially C₁₋₄alkoxy), hydroxy,sulphamoyl, amine (especially —NHR¹⁰ and NR¹⁰Ar), mercapto, thioalkyl(especially C₁₋₄thioalkyl), cyano, ester (especially OCOR¹⁰ or COOR¹⁰)and amide (especially CONHR¹⁰ and NHCOR¹⁰);

where R¹⁰ is H or optionally substituted C₁₋₆alkyl (especially H orC₁₋₄alkyl) and Ar is an optionally substituted aromatic ring (especiallya benzene ring).

More preferred optional substituents and/or carbyl derived groups inFormula (1) are selected from SO₃M, CO₂M, PO₃M₂, Cl, Br, F, OH,C₁₋₄alkyl, C₁₋₄alkoxy, CONH₂, SO₂NH₂, OCO(C₁₋₄alkyl), COO(C₁₋₄alkyl),NHAr and NHCO(C₁₋₄alkyl), where M and Ar are as defined herein.

Certain compounds and/or moieties therein (such as repeat units), whichcomprise the present invention may exist in many different forms forexample at least one form from the following non-exhaustive list: salts(e.g. with organic and/or inorganic acids and/or bases including acidand/or base addition salts); isomers, stereoisomers, enantiomers,diastereoisomers, geometric isomers, tautomers, conformers, zwitterions,forms with regio-isomeric substitution, isotopically substituted forms,polymorphs, polymeric configurations, tactic forms, interstitial forms,complexes, chelates, clathrates, interstitial compounds,non-stoichiometric complexes, stoichiometric complexes, ligandcomplexes, organometallic complexes, solvates, isotopic forms, mixturesthereof and/or combinations thereof within the same species. The presentinvention preferably comprises all such forms of compounds, polymers,moieties therein, any compatible mixtures thereof and/or anycombinations thereof, which comprise the present invention, preferablythose which are effective in IJP and/or colour filters.

Salts of Formula (1) may be formed from one or more organic and/orinorganic bases. Preferred salts of Formula (1) are soluble in water.

The inks preferably contain from 1 to 10, more preferably from 1 to 6,especially from 1 to 3, more especially 1 compound of Formula (1).

The compounds of Formula (1) are preferably soluble in water. However,they may be modified to be soluble in organic solvents by use of a QACas the counter ion, where QAC is as hereinbefore defined.

The compounds of Formula (1) may be prepared by any suitable methodknown in the prior art.

The composition may contain further compounds other than those ofFormula (1), for example to modify the colour or brightness of the ink.

The compounds of Formula (1) may be used individually as part of a YMC(yellow, magenta, cyan) colour filter, or mixed with other compounds asthe red or green component of an RGB (red, green, blue) colour filter.The arrangement of pixels could be any of those known in the art(stripe, mosaic, delta) and the filters would be suitable for displays,especially LCD's, and solid state imaging devices.

Use of the compounds of Formula (1) gives filters with very goodfastness properties and brighter than those in the prior art.

The compounds may also be used in an ink-jet printing ink to give brightyellow prints with good fastness properties.

It is another object of the present invention to provide improved inksfor processes for forming film coatings, that overcome some or all ofthe disadvantages of the prior art as discussed above, as well asproducts made and coated by processes using such inks (in particularcolour filters). In particular there is provided a composition accordingto the first aspect of the invention which is a green, red or yellow inksuitable for use in any of these processes.

Therefore according to another aspect of the present invention, there isprovided an ink containing a compound of Formula (1) for use in anyprocess for preparing a patterned, cross-linked, polymer, film coatingon a substrate.

It is particularly preferred that the inks of the current invention areused in processes to manufacture a colour filter. These processes maycomprise or consist of steps known in methods for producing colourfilters (with colorants other than the novel compounds of the presentinvention). Such processes are well known in the art and include variousprinting, photolithographic, photographic, electrodeposition, laserablation and thermal transfer processes. Examples of suitable processesare described below and in the following references, but it is to beunderstood that the invention is not limited to these processes:

“Reliability Improvements of Dichromated Gelatin Color Filters forTFT-LCD's”, A. Endo, E. Hirose, T. Sato, S. Otera, N. Chiba, Polym.Mater. Sci. Eng., 1990, 63, 472-6.

“Process and Material for Color Filter Preparation in Liquid CrystalDisplay”, H. Aruga, J. Photopolym. Sci. Technol., 1990, 3, 9-16.

“Color Filter for Liquid Crystal Display”, S. Okazaki, Trans. Inst.Electron. Inf. Commun. Eng., Sect. E, 1988, E71, 1077-9.

P. Gregory, Chapter 2 “Micro Color Filters” in “High-TechnologyApplications of Organic Colorants”, Kluwer Academic/Plenum Publishers,1991.

“Color Filters for LCDs”, K. Tsuda, Displays, 1993, 14, 115-24.

“Printing Color Filter for Active Matrix Liquid Crystal Display ColorFilter”, K. Mizuno, S. Okazaki, Jpn. J Appl. Phys., Part 1, 1991, 30,3313-17.

EP 661350 (=U.S. Pat. No. 5,608,091) (Nippon Shokubai)

EP 833203 (Nippon Shokubai)

It will be appreciated that where the compounds described are not watersoluble, the processes described in the references may need appropriatemodification to allow the use of the compositions and compounds of thepresent invention. Alternatively, where the colorants described aresolvent soluble dyes, compositions and compounds of the presentinvention may be used by modification of their solubility in organicsolvents through appropriate choice of the counter ion as describedpreviously.

A typical process for preparing a patterned, cross-linked, polymer, filmcoating on a substrate comprising the steps of

(a) applying to the substrate simultaneously and/or sequentially in anyorder.

(i) one or more cross-linkable polymer precursor(s);

(ii) optionally one or more additional cross-linker(s) capable ofcross-linking the precursor(s) for the polymer(s); and

(iii) one or more compound(s) of Formula (1) optionally with one or moreother colorant(s);

(b) optionally patterning one or more non cross-linked film(s) ofcomponent (i); component (ii); component (iii) and/or mixture(s)thereof, optionally before application of further components; and

(c) initiating cross-linking the mixture of components (i), (ii) insitu, to form an optionally patterned, cross-linked polymeric filmcoating on the substrate.

Preferably the application method in step (a) comprises applying an inkcomprising both components (i) and (ii).

It is also preferred that the polymer precursor(s) in step (a) (i) abovecomprise water dissipatable polymer precursor(s). It is especiallypreferred that these water dissipatable polymer precursor(s) compriseacrylic polymer precursor(s).

A process for which the present invention is particularly suitable is aprinting process, especially an ink-jet printing (IJP) process.

Preferably the printing process used is thermal or piezo IJP. Theprinciples and procedures for ink jet printing are described in theliterature for example in High Technology Applications of OrganicColorants, P. Gregory, Chapter 9 ISBN 0-306-43637-X.

Other suitable printing methods comprise: flexographic printing; off-setprinting [e.g. as described in JP-A-10(98)-088055 (Sumitomo Rubber)]lithographic printing; gravure printing; intaglio printing; dyediffusion thermal transfer, screen and/or stencil printing [e.g. asdescribed in WO 97-048117 (Philips Electronics)] and/or using‘typographic ink imaging pins’ (e.g. as described in WO 97-002955(Coming Inc.)].

Preferred methods of applying the polymer precursor and compound ofFormula (1) to the substrate comprise one or more of the following:

1) print onto the substrate (advantageously by IJP) a mixture comprisingthe polymer precursor which is thermally cross-linkable and thecolorant; and thereafter curing the mixture in situ (e.g. as describedin the applicant's co-pending application GB 9824818.0).

2) Apply to the substrate a polymer precursor which is an anioniccolourable photosensitive resin, and then exposing the resin to UV lightvia a mask to either make the exposed portions, which correspond to thepixels accept colorant; or harden the resin at the exposed portions,which correspond to the black matrix, to make it resistant to colorant;and print onto the resin (advantageously by IJP) a solution of thecolorant. [e.g. as described in EP 0703471(Canon)]:

An additional method of applying the ink is by a photolithographicprocess. This may involve either

1) Apply to a substrate a polymer precursor which is an anioniccolourable photosensitive resin; and then expose the resin to radiation(e.g. UV light) through a patterned mask, develop the substrate toremove unexposed portions of the resin, optionally heat to further setthe resin, then dip the substrate into an aqueous solution of thecolorant. [e.g. as described in U.S. Pat. No. 5,190,845 (Nippon Kayaku)]

2) Apply to a substrate an ink containing a photosensitive resin and thecolorant; and then expose the resin to radiation (e.g. UV light) througha patterned mask, develop the substrate to remove either the exposed orunexposed portions of the resin and optionally heat to further set theresin [e.g as described in EP 564237 (Mitsui Toatsu)]

3) Apply to a substrate a non-photosensitive ink containing the colorantand a thermally cross-linkable resin; then apply an ink containing aphotosensitive resin over this coloured film; expose the photosensitiveresin to radiation (e.g. UV light) through a patterned mask; develop thesubstrate to remove either the exposed or unexposed portions of thephotosensitive resin and the corresponding portions of the coloured filmbeneath, heat to thermally cure the coloured polymeric film andoptionally strip the photosensitive resin that remains [e.g. asdescribed in U.S. Pat. No. 5,176,971 (Kyodo Printing) and WO 88/05180(Brewer Science Inc.)]

In 1) the photosensitive resin may be either a natural polymer such asgelatin or casein which has been photosensitised by the addition of forexample ammonium dichromate, or may be a synthetic polymer.

In 2) and 3) the photosensitive resins used may be of either thepositive or negative type. In the positive type, the solubility of theresin in a developing solution increases on exposure to radiation; inthe negative type the solubility of the resin in a developing solutiondecreases on exposure to radiation.

In the laser ablation method, an ink containing a compound of Formula(1) and a (optionally thermally curable) non-photosensitive resin isapplied to the substrate, then portions of the substrate are irradiatedwith a laser beam to selectively remove the ink in those areas throughvaporisation and the remaining ink is optionally heated to thermallycure the resin [e.g. as described in JP10274709 (Sekisui Chem Ind.)]

In these processes the inks may be applied to the substrate by any knowncoating method including spin-coating, bar-coating, dip-coating,curtain-coating, roller-coating and electrospray.

The process of the present invention can be used to give optionallypatterned, optionally transparent films and coatings on substrates ingeneral, including substrates which are not transparent. Accordingly thepresent invention includes a process for preparing polymeric filmcoatings for substrates in general not just colour filters.

The cross-linked polymeric film coating may be formed on a substrate towhich the coating will bond, adhere, absorb or fuse. Preferably (e.g. ifthe process of the present invention is used to manufacture a colourfilter) the substrate is transparent. Suitable transparent substratesinclude glass; plastics films and plates such as those ofpolyvinylalcohol, polyester, polyvinylchloride, polyvinylfluoride,polycarbonate, polystyrene, polyamide or polyimide. The substrate may beflexible or may be a flat panel (e.g. as used in many LCD displays). Apreferred substrate is glass.

The substrates may be pre-treated to improve bonding, adhesion,absorption, fusion or spreading of the cross-linked polymeric coating onthe substrate. Suitable pre-treatments include plasma etching in whichthe substrate is placed in an oxygen atmosphere and subjected to anelectrical discharge or application of an adhesion promoter such as asilane.

An ink suitable for manufacture of a colour filter according to thepresent invention may be made by any method known in the art andcomprise: one or more compounds(s) of Formula (1), one or more solventsand optionally other formulating agents. The inks may in additioncontain precursor(s) for cross-linked polymer(s), one or morecross-linker(s) capable of cross-linking the precursor(s), optionallyone or more non cross-linkable polymer(s) for improving the film-formingability of the inks or the properties of the final films and (asappropriate for chemically or photochemically initiated systems) eithera radical source, a photopolymerisation initiator or a dissolutioninhibitor. An ink coloured in one of the desired colours can be producedwith compounds of the present invention and optionally one or more othercolorants, typically either yellow, green or red.

Preferably the optionally patterning method in step (b) of the processof the present invention uses electromagnetic radiation, more preferablyUV radiation. Optionally to produce a colour filter the pattern formedmay comprise of a multiplicity of discrete filter regions (pixels) on atransparent substrate via a single pass ink-jet printing process.Optionally, the transparent substrate has previously been subdividedinto discrete pixel regions by any method known in the art (for exampleformation of a black matrix by photolithography).

The steps of the process of the present invention described herein maybe followed for each of the desired colours to form a multi-colouroptical filter structure so that the filter structure finally comprisesthe transparent substrate and a single layer of differently colouredpixels arranged in triads or in any desired groups, each consisting of apredetermined number of differently coloured pixels.

The inks of the present invention are particularly useful for formingthe green and red pixels of an additive (red, green and blue [RGB])colour filter and for forming the yellow pixels of a subtractive(yellow, magenta and cyan [YMC]) colour filter.

A further aspect of the invention provides a process for printing animage on a substrate comprising applying thereto an ink according toanother aspect of the present invention, preferably by printing, morepreferably by means of an ink jet printer. Preferably the ink comprisessolvent (preferably aqueous) and a compound of Formula (1) as describedherein.

The ink jet printer preferably applies the ink to the substrate in theform of droplets which are ejected through a small nozzle onto thesubstrate. Preferred ink jet printers are piezoelectric ink jet printersand thermal ink jet printers. In thermal ink jet printers, programmedpulses of heat are applied to the ink in a reservoir (e.g. by means of aresistor adjacent to the nozzle) thereby causing the ink to be ejectedin the form of small droplets directed towards the substrate duringrelative movement between the substrate and the nozzle. In piezoelectricink jet printers the oscillation of a small crystal causes ejection ofthe ink from the nozzle. The term ink-jet printer denotes any devicewhich could use an IJP technique to produce an image.

A further aspect of the present invention provides a substrate which hasapplied thereon an ink of the present invention as defined herein and/orwhich has been prepared by the process of the present invention also asdefined herein.

The substrate, which is optionally transparent, preferably comprisesplastic, metal, glass, paper, an overhead projector slide and/or atextile material. More preferably for a colour filter the substrate isglass. Preferred textile materials for ink jet printing are cotton,polyester and blends thereof. When the substrate is a textile materialthe process for printing an image thereon according to the inventionpreferably further comprises the step of heating the resultant printedtextile, preferably to a temperature of 50° C. to 250° C.

According to a further feature of this invention there is provided acolour filter comprising red, green and blue filter elements, or yellow,magenta and cyan filter elements, characterised in that the colourfilter carries a compound of Formula (1). Preferably the color filterfurther comprises a coloured cross-linked polymeric coating on atransparent substrate and/or a transparent, coloured, cross-linked,polymer coating on a substrate prepared by the processes according tothe present invention.

More preferably the substrate or colour filter comprises an array ofcoloured trichromatic elements in which the trichromat is selected from:a red, green and blue trichromat; and a cyan, magenta and yellowtrichromat.

Preferably the substrate or colour filter has utility as a component fora coloured display.

A further feature of the invention comprises a display containing asubstrate or colour filter prepared according to the present invention.Preferably the display comprises a liquid crystal display.

A further feature of the present invention provides a cartridge suitablefor use in an ink jet printer containing an ink according to theinvention. Also there is provided an ink jet printer containing an inkaccording to the invention.

The compounds of the present invention are particularly useful as yellowdyes which form particularly good green colorants when combined with afurther cyan dye or pigment. Such compositions are particularly usefulto produce a green colour filter For the purposes of the presentinvention the term ‘colorant’ as used herein denotes perceptible and/oremissive materials. The term “perceptible material” as used hereinincludes all dyes and/or pigments and denotes materials which absorbradiation substantially in that part of the electromagnetic (EM)spectrum which encompass the infra red (IR); visible and/or ultraviolet(UV) regions, preferably in a region where the radiation wavelength [λ]is from about 200 nm to about 800 nm, more preferably in the visibleregion which is detectable by the normal, unaided human eye. The term“emissive material” as used herein denotes a material which is capableof emitting radiation, preferably EM radiation, more preferablyradiation in the IR, visible and/or UV regions of the EM spectrum.Examples of emissive materials comprise fluorescent, phosphorescentand/or radioactive materials.

Therefore broadly in another aspect of the present invention there isprovided a coloured composition comprising a compound of Formula (1) or(2) (as described herein) together with one or more cyan or green dye(s)and/or one or more cyan or green pigments(s).

Preferably the cyan or green dye comprises a water soluble metalphthalocyanine, more preferably a copper, zinc, aluminium and/or nickelphthalocyanine. Preferably the composition of the present inventioncomprises a cyan dyes of Formula (3)

in which:

T represents H or an optional substituent, preferably H, alkyl, alkoxy,CO₂M, SO₃M;

V represents CO₂M, SO₃M or PO₃M₂, especially meta-CO₂M x and yindependently represent from 0 to 4, preferably from 1 to 3; and

x+y is from 3 to 5, preferably 4;

where M is as given herein for compounds of Formula (1) herein.

Where the cyan or green colorant is a pigment, preferred pigmentsinclude C.I. Pigment Green 7 and C.I. Pigment Green 36.

The colorants of the present invention may also be used as shadingcomponents in combination with red, magenta and/or orange colorants toproduce good red colorants which are useful for producing a red colourfilter.

Therefore, in another aspect of the present invention there is provideda coloured composition comprising a compound of Formula (1) (asdescribed herein) together with one or more red, magenta and/or orangecolorant(s), [e.g. dye(s) and/or pigment(s)].

It is also to be understood that one or more further yellow colorant(s),[e.g. dye(s) and/or pigment(s)] other than those of the currentinvention, may be present in the ink for the purpose of adjusting theshade or enhancing the fastness properties of the ink and the resultantfilm or image produced using the ink.

Apart from the colorants of the present invention of Formula (1) and(2), compositions, inks, colour filters and processes of the presentinvention may comprise at least one further colorants to form a colorantmixture.

The further colorants (as well as colorants of the present invention)are preferably compatible with the resultant cross-linked polymercoatings, i.e. the resultant cured films have high transparency. Wherethe colorant is a dye, preferably the colorant is insoluble in organicsolvents and soluble in water, for example the colorant may containsulpho, phospho or carboxy groups.

If the colorant used is not soluble in the solvent used for the ink, thecolorant is preferably present as a fine dispersion, prepared by forexample milling the colorant in a solvent in a horizontal shaker in thepresence of glass or metal beads and a dispersant. Suitable dispersantsmay comprise an anionic type (for example lignosulphonates and othersulphonated aromatic species) or a non-ionic type (for example alkyleneoxide adducts).

Useful classes of further colorants include azos (including metallisedazos), anthraquinones, phthalocyanines, perylenes, quinacridones,diketopyrrolopyrroles, pyrrolines, thiophenedioxides,triphenodioxazines, methines, benzofuranones, benzodifuranones,coumarins, indoanilines, benzenoids, xanthenes, triphenylmethanes,nitros, nitrosonaphthols, phenazines, solvent soluble sulphur dyes,quinophthalones, pyridones, aminopyrazoles, pyrollidines, pyrroles,styrylics, maleimides, triphenazonaphthylamines, styryls, dithienes,azomethines, cyanines, indanthrones, benzimidazolones, isoindolinones,isoindolines and azoics.

The Colour Index International lists suitable dyes and pigments for useas further colorants such as acid dyes, direct dyes, basic dyes,reactive dyes, solvent dyes, disperse dyes and pigments and furtherexamples of acid dyes are given in the Colour Index, 3rd Edition, Volume1, pages 1003 to 1561, further examples of direct dyes are given inVolume 2, pages 2005 to 2478, further examples of basic dyes are givenin Volume 1, pages 1611 to 1688, further examples of reactive dyes aregiven in Volume 3 pages 3391 to 3560, further examples of solvent dyesare given in Volume 3, pages 3563 to 3648, further examples of dispersedyes are given in Volume 2, pages 2479 to 2742, and further examples ofpigments are given in Volume 3 pages 3267 to 3390. These colorants areincluded herein by reference.

Preferably the further colorant(s) is selected from at least one cyan,green, red, magenta and/or orange colorant which is a dye or a pigment.

Subject to the provisos herein, generally preferred colorants arepigments; or dyes which have substituent groups which aid the solubilityof the dye(s) in liquid media used in the process or which aid thesolubility of the dye(s) in the final cross-linked polymer matrix.

Preferably the composition is an the ink comprising:

(a) from 0.01 to 30 parts of a compound of Formula (1); and

(b) from 70 to 99.99 parts of a liquid medium or a low melting pointsolid medium; wherein all parts are by weight and the number of parts of(a)+(b)=100.

The number of parts of component (a) is preferably from 0.1 to 20, morepreferably from 0.5 to 15, and especially from 1 to 5 parts. Compound Ais preferably an IJP effective compound of Formula (1) more preferablyof Formula (2). The number of parts of component (b) is preferably from99.9 to 80, more preferably from 99.5 to 85, especially from 99 to 95parts.

When the medium is a liquid, preferably component (a) is completelydissolved in component (b). Preferably component (a) has a solubility incomponent (b) at 20° C. of at least 10%. This allows the preparation ofconcentrates which may be used to prepare more dilute inks and reducesthe chance of the colorant precipitating if evaporation of the liquidmedium occurs during storage.

Preferred liquid media include water, a mixture of water and a watermiscible organic solvent.

When the medium comprises a mixture of water and an organic solvent, theweight ratio of water to organic solvent is preferably from 99:1 to1:99, more preferably from 99:1 to 50:50 and especially from 95:5 to80:20. The liquid medium may comprise water and preferably two or more,more preferably from 2 to 8, water-soluble organic solvents.

The water-miscible organic solvent(s) may comprise any of the followingand/or mixtures thereof: C₁₋₆-alkanols, preferably methanol, ethanol,n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol,n-pentanol, cyclopentanol and/or cyclohexanol; amides, preferably linearamides, for example dimethylformamide and/or dimethylacetamide; ketonesand/or ketone-alcohols, preferably acetone, methyl ether ketone,cyclohexanone and/or diacetone alcohol; water-miscible ethers,preferably C₂₋₄ethers, tetrahydrofuran and/or dioxane; diols, preferablyalkylene glycols containing a C₂-C₆ alkylene group; more preferablyC2-12diols (for example pentane-1,5-diol, ethylene glycol, propyleneglycol, butylene glycol, pentylene glycol, hexylene glycol); thioglycolspreferably thiodiglycol; oligo- and/or poly-alkyleneglycols (for examplediethylene glycol, triethylene glycol, polyethylene glycol and/orpolypropylene glycol); triols, preferably glycerol and/or1,2,6-hexanetriol; lower alkyl glycol and polyglycol ethers, preferablyC₁₋₄alkyl ethers of diols or monoC₁₋₄alkyl ethers of C₂₋₁₂diols: {forexample 2-methoxyethanol, 2-(2-methoxyethoxy)ethanol,2-(2-ethoxyethoxy)ethanol, 2-(2-butoxyethoxy)ethanol,3-butoxypropan-1-ol, 2-[2-(2-methoxyethoxy)ethoxy]ethanol,2-[2-(2-ethoxyethoxy)ethoxy]ethanol and/or ethyleneglycol monoallylether}; cyclic amides, preferably optionally substituted pyrrolidones(for example 2-pyrrolidone, N-methyl-2-pyrrolidone,N-ethyl-2-pyrrolidone, caprolactam and/or 1,3-dimethylimidazolidone);cyclic esters, preferably caprolactone; sulphoxides, preferably dimethylsulphoxide and/or sulpholane.

More preferred water-soluble organic solvents are selected from: cyclicamides (for example 2-pyrrolidone, dimethyl pyrrolidone,N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidoneN-(2-hydroxyethyl)-2-pyrrolidone and mixtures thereof.); diols, (forexample 1,5-pentane diol, ethyleneglycol, thiodiglycol, diethyleneglycoland triethyleneglycol); C₁₋₆alkyl ethers of diols (for example2-methoxy-2-ethoxy-2-ethoxyethanol); C₁₋₆-alkyl mono ethers ofC₂₋₆-alkylene glycols; C₁₋₆-alkyl mono ethers of poly(C₂₋₆-alkyleneglycols); and mixtures thereof.

A preferred liquid medium comprises:

(a) from 75 to 95 parts water; and

(b) from 25 to 5 parts in total of one or more solvents selected from:diethylene glycol, 2-pyrrolidone, thiodiglycol, N-methylpyrrolidone,cyclohexanol, caprolactone, caprolactam and pentane-1,5-diol;

where the parts are by weight and the sum of the parts (a)+(b)=100.

Another preferred liquid medium comprises:

(a) from 60 to 80 parts water;

(b) from 2 to 20 parts diethylene glycol; and

(c) from 0.5 to 20 parts in total of one or more solvents selected from:

2-pyrrolidone, N-methylpyrrolidone, cyclohexanol, caprolactone,caprolactam, pentane-1,5-diol and thiodiglycol;

where the parts are by weight and the sum of the parts (a)+(b)+(c)=100.

When the liquid medium comprises an organic solvent free from water,(i.e. less than 1% water by weight) the solvent preferably has a boilingpoint of from 30° to 200° C., more preferably of from 40° to 150° C.,especially from 50 to 125° C. The organic solvent may bewater-immiscible, water-miscible or a mixture of such solvents.Preferred water-miscible organic solvents comprise any of thosedescribed above and mixtures thereof. Preferred water-immisciblesolvents comprise aliphatic hydrocarbons; esters (for example ethylacetate) chlorinated hydrocarbons (for example dichloromethane), ethers(for example diethyl ether) and mixtures thereof.

When the liquid medium comprises a water-immiscible organic solvent,preferably it comprises a polar solvent (for example a C₁₋₄alkanol) toenhance the solubility of the dye in the liquid medium. It is especiallypreferred that where the liquid medium is an organic solvent free fromwater it comprises a ketone (especially methyl ethyl ketone) and/or analcohol (especially a C₁₋₄alkanol, more especially ethanol or propanol).

The organic solvent free from water may be a single organic solvent or amixture of two or more organic solvents. It is preferred that when themedium is an organic solvent free from water it is a mixture of 2 to 5different organic solvents. This allows a medium to be selected whichgives good control over the drying characteristics and storage stabilityof the ink.

Ink media comprising an organic solvent free from water are particularlyuseful where fast drying times are required and particularly whenprinting onto hydrophobic and non-absorbent substrates, for exampleplastics, metal and glass.

Preferred low melting solid media have a melting point in the range from60° C. to 125° C. Suitable low melting point solids include long chainfatty acids or alcohols, preferably those with C₁₈₋₂₄chains, andsulphonamides. The compound of Formula (1) may be dissolved in the lowmelting point solid or may be finely dispersed in it.

The ink may also contain additional components conventionally used ininks for IJP, for example viscosity and surface tension modifiers,corrosion inhibitors, biocides, kogation reducing additives andsurfactants which may be ionic or non-ionic.

In a further aspect of the present invention there is provided a generalpurpose ink optionally for use in preparing a colour filter, the inkcomprising a fluid medium, and one or more compounds of Formula (1)herein. The precursor(s), cross-linker(s) and colorant(s) are as definedpreviously.

Preferably inks according to the invention are prepared by mixingtogether (i) a solution of the compound(s) of Formula (1) and optionallywater.

The amount of the compound(s) or Formula (1) and solvent contained inthe ink will vary according to the depth of shade required. Typically,however, the ink will comprise

(a) from 0.5 to 15 parts, more preferably 0.8 to 10 parts, especially 1to 8 parts in total of one or more compounds of Formula (1);

(b) from 0 to 90 parts, more preferably from 50 to 80 parts of water;and

(c) from 0 to 90 parts, more preferably 0 to 60 parts of one or morewater miscible organic solvent(s); and

(d) other ingredients from 0 to 50 parts, more preferably 0 to 30;

where all parts are by weight and the total number of parts of(a)+(b)+(c)+(d) add up to 100.

The water-miscible solvent may be one or more of those described herein,preferably with a solubility in water at 20° C. of more than 50 g/l.

Instead of parts (b) and (c) [the water and water-miscible organicsolvent(s)] the ink may comprise one or more water-immiscible organicsolvent(s).

Suitable water-immiscible organic solvents include aromatichydrocarbons, e.g. toluene, xylene, naphthalene, tetrahydronaphthaleneand methyl naphthalene; chlorinated aromatic hydrocarbons, e.g.chlorobenzene, fluorobenzene, chloronaphthalene and bromonaphthalene;esters, e.g. butyl acetate, ethyl acetate, methyl benzoate, ethylbenzoate, benzyl benzoate, butyl benzoate, phenylethyl acetate, butyllactate, benzyl lactate, diethyleneglycol dipropionate, dimethylphthalate, diethyl phthalate, dibutyl phthalate, di (2-ethylhexyl)phthalate; alcohols having six or more carbon atoms, e.g. hexanol,octanol, benzyl alcohol, phenyl ethanol, phenoxy ethanol, phenoxypropanol and phenoxy butanol; ethers having at least 5 carbon atoms,preferably C₅₋₁₄ ethers, e.g. anisole and phenetole; nitrocellulose,cellulose ether, cellulose acetate; low odour petroleum distillates;turpentine; white spirits; naphtha; isopropylbiphenyl; terpene;vegetable oil; mineral oil; essential oil; and natural oil; and mixturesof any two or more thereof.

The water-immiscible solvent preferably has a solubility in water at 20°C. of up to 50 g/l.

A further feature of the invention provides a composition comprising awater-dissipatable polymer and a compound of Formula (1). In thesecompositions the preferred water-dissipatable polymers and dyes are asdescribed in in the following co-pending patent applications WO95/34204,WO99/50326, WO99/50362, WO99/50361, WO00/29493, WO00/37575. Theseapplications are hereby incorporated by reference These applications arehereby incorporated by reference.

Such compositions may be dissipated in water and optionally mixed withfurther ingredients to give an ink, for example with one or more organicsolvents.

The other ingredients may comprise one or more formulating agentsconventionally used in inks for example to improve the solubility ofcolorant in the ink and/or to improve the flow and handling propertiesof the ink. Thus for example the ink may comprise one or more:humectant(s); rheological agent(s) [such as viscosity modifier(s) and/orsurface tension modifier(s), for example wax(es) (e.g. beeswax) and/orclay(s) (e.g. bentonite)]; corrosion inhibitor(s), biocides (such asthose available commercially from Avecia Limited under the trade nameProxel GXL or from Rohm and Haas under the trade name Kathon);fungicide(s); kogation reducing additives; IR absorber(s) (such as thatavailable commercially from Avecia Limited under the trade name Projet900NP); fluorescent brightener(s), (such as C.I. Fluorescent Brightener179); and surfactant(s) (which may be ionic or non-ionic and includesurface active agent(s) wetting agent(s) and/or emulsifier(s) such asthose described in McCutcheon's Emulsifiers and Detergents 1996International Edition or in Surfactants Europa 3^(rd) Edition 1996 eachof which is incorporated herein by reference).

The ink may also comprise radical scavengers and/or UV absorbers to helpimprove light and heat fastness of the ink and resultant colour filter.Examples of such additives include:2-hydroxy-4-methoxy-5-sulfobenzophenone; hydroxy phenylbenzotriazole;4-hydroxy-TEMPO and transition metal complexes (such as nickel complexesof thiocarbamic acids). These additives are used typically in an amountfrom 30% to 60% by weight of the colorant, and are further described in“The Effect of Additives on the Photostability of Dyed Polymers”, Dyesand Pigments, 1997, 33(3), 173-196 and JP-A-04-240603 (Nippon Kayaku).

For an aqueous ink, the ink preferably has a pH from 3 to 12, morepreferably from 4 to 11. The pH selected will depend to some extent onthe desired cation for the colorant and the method of application. Thedesired pH may be obtained by the addition of a pH adjusting agent suchas an acid, base or pH buffer. The amount of pH adjuster used will varyaccording to the desired pH of the ink, but typically a base may bepresent in an amount of up to 30%. Where a liquid(s) is added to themixture the printed substrate may be dried by heating or by air dryingat ambient temperature to evaporate the liquid before the coating iscured or during curing.

Examples of suitable formulations of polymer precursor and colorantwhich may be used in the method of the present invention are also givenin the applicant's co-pending applications GB 9824818.0 and EP 0764290,where it will be appreciated that the colorants of Formula (1) hereinreplace some or all of the colorants used in these prior artformulations.

Preferably the ink of the present invention comprises from about 10 toabout 99.6, preferably from about 30 to about 99.5, more preferably fromabout 50 to about 99, parts of the liquid medium; and from about 90 toabout 0.4 parts, preferably from about 70 to about 0.5, more preferablyfrom about 50 to about 1, parts of the other ingredients; where allparts are by weight and the number of parts totals 100.

The inks according to a further aspect of the invention may be preparedby mixing the ingredients in any order. Suitable mixing techniques arewell known in the art, for example agitation, ultrasonication orstirring of the components. The ingredients may be present in the ink inany form suitable for application to the substrate, for example the formof a dispersion, emulsification, suspension, solution or a combinationthereof.

Examples of further media for inks of the present invention comprising amixture of water and one or more organic solvents are described in U.S.Pat. No. 4,963,189, U.S. Pat. No. 4,703,113, U.S. Pat. No. 4,626,284 andEP 0425150A.

Dyes of the invention will now be illustrated by the following examplesin which all parts and percentages are by weight unless specifiedotherwise. In the Examples (and previously), compounds referred to byreference to CI numbers are the dyestuffs identified by these numbers inthe Colour Index International, 3^(rd) Edition, 3^(rd) Revision. In eachof the following Examples, the inks were tested and the results were setout in tables.

EXAMPLE 1

Preparation of:

Stage 1(a)

Preparation of the PyridoneCoupler:1-(2′-Hydroxyethoxyethyl)-3-cyano-4-methyl-6-hydroxy-2-pyridone

Ethylcyanoacetate (115 parts) was slowly added to2-(2-aminoethoxy)ethanol (134 parts) with stirring, while maintainingthe temperature below 30° C. On completion of the addition, the mixturewas heated at 95° C. for 3 hours then cooled back to room temperature.Methyl acetoacetate (123 parts) was added, maintaining the temperaturebelow 30° C., the whole mixture was then cooled to 10° C. before addingethylamine (57.6 parts). The resultant mixture was heated at 90° C. for18 hours, then cooled to room temperature. On acidification to pH1 withconcentrated hydrochloric acid, the product precipitated out. This wasisolated by filtering, washing with a small amount of 2N HCl and finallydrying at 60° C. to yield 81 parts of the above pyridone coupler.

Stage 1(b)

Preparation of Title Compound

2-Amino-4-sulphobenzoic acid (27.2 parts) was stirred in water (200parts) at pH5 until dissolved. The solution was cooled to <10° C. andconcentrated HCl (47 parts) was added. Sodium nitrite (6.8 parts) wasslowly added and the reaction mixture was stirred at 0-10° C. for 30minutes. Excess nitrous acid was then removed by addition of sulphamicacid, until the diazo mixture was negative to starch-iodide. To this wasadded a solution of the pyridone coupler (53 parts) from Stage 1 (a) inwater (200 parts), which had been adjusted to pH8 with 2N NaOH. Thetemperature of the reaction mixture was maintained below 10° C. duringthe addition. The mixture was then stirred for 16 hours whilst warmingto room temperature. The dark yellow solution was acidified to pH 1 withconcentrated HCl and the resultant precipitate was collected byfiltration. The precipitate was re-dissolved in water (200 parts), andadjusted to pH9 with 0.88 S.G. ammonia. The product was thenre-precipitated by pouring on to concentrated HCl (35 parts) andcollected by filtration. The product was dissolved in ammonia andre-precipitated and collected by filtration once more. Finally theproduct was dissolved in water (200 parts) containing ammonia at pH9,dialysed to remove the inorganic components, screened through a 0.45μfilter and dried at 60° C. to yield the title compound as a yellowpowder of its ammonium salt (7.7 parts).

The following dyes were made by an analogous method to that described inExample 1:

Ex R¹ R² R³  2 H SO₃H ^(n)Bu  3 SO₃H H ^(n)Bu  4 H SO₃H 2-Ethylhexyl  5SO₃H H 2-Ethylhexyl  6 H SO₃H C₂H₄OH  7 H SO₃H C₂H₄NH₂  8 H SO₃HCH₂C(CH₃)₃  9 H SO₃H C₂H₄Oet 10 H SO₃H Cyclohexyl 11 H SO₃H n-Hexyl 12 HSO₃H C₃H₆Oet 13 H SO₃H C₅H₁₀OH 14 SO₃H H C₂H₄OC₂H₄OH 15 SO₃H H C₃H₆OH 16SO₃H H C₂H₄Oet

Example 17

Preparation of

Stage 17(a)

Preparation of the PyridoneCoupler:1-^(n)Butyl-3-carbonamido-4-methyl-6-hydroxy-2-pyridone

1-^(n)Butyl-3-cyano-4-methyl-6-hydroxy-2-pyridons (103 parts) was addedcarefully to 1.84 S.G. sulphuric acid (370 parts), maintaining thetemperature below 50° C. After the addition was complete the temperaturewas raised to 75° C. for 12 hours. The reaction mixture was allowed tocool to room temperature, then drowned out onto ice (400 parts). Thesolution was carefully neutralised with calcium carbonate and screened;the solids were further washed through with copious amounts of water andethanol. Finally, the solution was evaporated to dryness under reducedpressure and the solids dried at 60° C. to give the above pyridonecoupler as a light gray powder (122 parts).

Stage 17(b)

Preparation of Title Compound

The title compound was made in an analogous manner to the dyestuff inExample 1, substituting a molar equivalent of the pyridone coupler fromStage 17(a) for the coupler used in Example 1 Stage 1(b), and a molarequivalent of 2-amino-5-sulphobenzoic acid for the diazo component usedin Example 1 Stage 1(b).

The following dyes were made by an analogous method to that described inExample 17:

Ex R¹ R² R³ 18 SO₃H H C₂H₅ 19 SO₃H H 2-Ethylhexyl 20 SO₃H H ^(n)Pr 21 HSO₃H ^(n)Pr 22 H SO₃H ^(n)Bu

Example 23

Preparation of

Stage 23(a)

Preparation of the Pyridone Coupler1-(^(n)Butyl)-4-methyl-6-hydroxy-2-pyridone

1-(^(n)Butyl)-3-cyano-4-methyl-6-hydroxy-2-pyridone (20.6 parts) wasadded slowly to 75% sulphuric acid (40.6 parts). After addition thesolution was heated at 125° C. for 3 hours then cooled back to roomtemperature. The thick oil was poured onto ice (200 parts) with goodstirring. 47% Sodium hydroxide solution was then carefully added untilthe product started to solidify. After stirring for a further 30minutes, the solid was collected by filtration and dried at 60° C. toyield the title pyridone coupler as a brown powder (17.5 parts).

Stage 23(b)

Preparation of Title Compound

The title compound was made in an analogous manner to the dyestuff inExample 1, substituting a molar equivalent of the pyridone coupler fromStage 23(a) for the coupler used in Example 1 Stage 1(b).

Example 24

Preparation of

Stage 24(a)

Preparation of the PyridoneCoupler:1-(2′-aminoethyl)-3-cyano4-methyl6-hydroxy-2-pyridone

This coupler was made in an analogous manner to that described inExample 1 Stage 1(a), substituting ethylene diamine (5 times molarexcess) for the 2-(2-aminoethoxy)ethanol.

Stage 24(b)

Preparation of the Intermediate:5-(2′-Carboxy-5′-sulphophenylazo)-1-(2′-aminoethyl)-3-cyano-4-methyl-6-hydroxy-2-pyridone

This intermediate was made in an analogous manner to the dyestuff inExample 1, substituting a molar equivalent of the pyridone coupler fromStage 24(a) for the coupler prepared in Example 1 Stage 1(a).

Stage 24(c)

Preparation of the Title Compound

Cyanuric chloride (2.6 parts) was dissolved in acetone (20 parts) andpoured onto ice/water (100 parts) at 0-5° C. A solution of metanilicacid (2.4 parts) in water (50 parts) at pH7 was then added to thecyanuric chloride suspension, maintaining the reaction at 0-5° C. andpH6. The mixture was stirred under these conditions for 2 hours. To thiswas then added a solution of5-(2′-carboxy-5′-sulphophenylazo)-1-(2′-aminoethyl)-3-cyano-4-methyl-6-hydroxy-2-pyridone(5.2 parts) prepared as described in Stage 24(b), in water (100 parts)at pH8.5, the mixture being stirred at pH8.5, 45° C. for 12 hours. Aftercooling to room temperature the solution was acidified to pH 1 withconcentrated HCl, and the solid was collected by filtration, dialysedand dried. This intermediate (8.7 parts) was then re-dissolved in water(400 parts) and ethanolamine (4.6 parts) was added. The solution wasthen heated at 70° C. for 6 hours. After cooling to room temperature,the product was precipitated by acidifying to pH 1 with concentrated HCland was collected by filtration. It was then re-dissolved in water (200parts), adjusted to pH9 with 0.88S.G. ammonia and re-precipitated bypouring on to concentrated HCl (35 parts). After stirring for 10 minutesthe product was collected by filtration then re-dissolved in ammonia andre-precipitated with concentrated HCl once more. After collection byfiltration, the product was dialysed, screened through a 0.45μ filterand dried at 60° C. to yield the ammonium salt of the title dye as ayellow powder (3.3 parts).

Example 25

Preparation of

Stage 25(a)

Preparation of the Intermediate PyridoneCoupler:1-^(n)Butyl-3-cyano-4-ethyl-6-hydroxy-2-pyridone

Ethylcyanoacetate (57 parts) was slowly added to n-butylamine (40 parts)with stirring, while maintaining the temperature below 30° C. Oncompletion of the addition, the mixture was heated at 95° C. for 3 hoursthen cooled back to room temperature. Methyl propionylacetate (65 parts)was then added followed by ethylamine (29 parts), maintaining thetemperature below 30° C. the whole time. The resultant mixture washeated at 90° C. for 18 hours, then cooled to room temperature. Thesolution was poured slowly on to ice (400 parts) and adjusted to pH1with concentrated hydrochloric acid to produce a sticky solid. Thesupernatant liquid was decanted off and the solid dried under vacuum toyield 80 parts of the above intermediate

Stage 25(b)

Preparation of the Pyridone Coupler:1-^(n)Butyl-3-cyanamido-4-ethyl-6-hydroxy-2-pyridone

The intermediate coupler (66 parts) from Stage 25 (a) was added slowlyto 1.84 S.G. sulphuric acid (220 parts), maintaining the temperaturebelow 50° C. After the addition was complete, the temperature was raisedto 70° C. for 8 hours. The reaction mixture was allowed to cool to roomtemperature, then drowned out into an ice/water mixture with vigorousstirring. The solid which precipitated out was isolated by filtrationand dried at 60° C. to yield the above coupler as an off-white powder(91 parts).

Stage 25(c)

Preparation of Title Compound

The title compound was made in an analogous manner to the dyestuff inExample 1, substituting a molar equivalent of the pyridone coupler fromStage 25(b) for the coupler prepared in Example 1 Stage 1(a), and amolar equivalent of 2-amino-5-sulphobenzoic acid for the diazo componentused in Example 1 Stage 1 (b).

For the purpose of evaluating the spectra and resistance properties offormulations containing the dyes, the inks were bar-coated on tomicroscope slides using a No.1 K-bar (RK Print-Coat Instruments Ltd.),and the slides cured at 200° C. for 15 minutes. The resultant films hada thickness of approximately 2 μm.

Example 26

Example 26 was prepared as in Example 24 except that in Stage 24 (c)5-aminosalicylic acid was used in place of metanilic acid

Comparative Dye A

Comparative dye A was prepared as in Stage 1(b) except that2-aminophenol-4-sulphonic acid was reacted with1-n-butyl-3-cyano-4-methyl-6-hydroxy-2-pyridone.

Comparative Dye B

Comparative dye B was prepared by forming a pyridone coupler as in Stage1 (a) except that 2-ethylhexylamine was used in place of2-(2-aminoethoxy)ethanol and then preparing the compound as in Stage1(b) except that aniline-2,5-disulphonic acid was used in place of2-amino-4-sulphobenzoic acid.

Comparative Dye C

Comparative dye C was prepared using the coupler as prepared ascomparative dye B but using 3-amino-4-sulphophenyl phosphonic acid inplace of 2-ethylhexylamine in Stage 1(b).

Comparative Dye D

Comparative dye D was prepared as in Example 6 of WO9829513.

Inks with the following formulation were made (all parts by weight):

Acrylic co-polymer (54% methyl methacrylate; 46% 13.2 parts methacrylicacid) Primid XL552 - ex EMS Chemie  4.4 parts2-Amino-2-methyl-1-propanol 13.2 parts Dye  3.0 parts Ammoniumdodecylbenzenesulphonate  0.9 parts Water 65.3 parts

The inks gave very bright yellow films with high transmission at 520 nmand low transmission at 420 nm. Transmission was determined bymeasuringthe spectra of the coloured films against a blank glass reference usinga Minolta CM-3600d spectrophotometer. Light fastness properties weremeasured using a xenon lamp in an Atlas weatherometer Ci35A (lamp power0.80 Wm⁻² at 420 nm, black panel 63° C., wet bulb depression 16° C.),and the ΔE values were determined using a Minolta CM-3600dspectrophotometer. The transmission and light fastness results aretabulated below.

Ink Ex Dye % T @ 420 nm % T @ 520 nm LF - ΔE/100 hours¹ 26 1 2 94 24.827 2 0 93 20.1 28 3 1 94 44.2 29 4 4 93 45.8 30 6 1 90 42.6 31 9 0 9028.5 32 11 0 93 45.3 33 12 1 95 30.2 34 13 4 96 30.0 35 14 0 89 41.2 3615 1 95 36.1 37 16 3 95 20.1 38 17 0 97 35.2 39 18 2 98 30.9 40 19 1 9833.4 41 20 0 98 40.9 42 21 2 99 48.5 43 22 0 98 30.1 44 23 0 98 43.8 4524 7 87 28.6 46 25 0 99 33.8 Comp. 1 A 14 65 77.3 Comp. 2 B 4 95 57.6

Example 47 and Comparative Example 3

Inks with the following formulation were made (all parts by weight):

Acrylic co-polymer (34% methyl methacrylate; 46% 13.2 parts methacrylicacid 20% hydroxyethyl methacrylate) Primid XL552 - ex EMS Chemie  4.1parts 0.88 S.G. ammonia 12.3 parts C.I. Reactive Blue 14  1.9 partsPyridone dye  3.3 parts Ammonium dodecylbenzenesulphonate  0.4 partsTriethyleneglycol monobutyl ether  0.9 parts Water 64.8 parts

The inks produced bright green highly transparent films, but the onemade using a dye of this invention had far superior light fastness:

Example Pyridone dye LF = ΔE/100 hrs 47 4 10.6 Comp 3 C 62.4

Examples 48 to 53

Inks similar to that used in Example 47 were made, using an alternativecyan component (all parts by weight):

Acrylic co-polymer (34% methylmethacrylate; 46% 11.5 parts methacrylicacid 20% hydroxyethyl methacrylate) Primid X1552 - ex EMS Chemie  3.9parts 0.88 S.G. ammonia 11.5 parts Cyan D¹ See Table Pyridone dye of thepresent invention See Table Ammonium dodecylbenzenesulphonate  0.4 partsTriethyleneglycol monobutyl ether  2.9 parts Water to 100 parts

All the inks produced bright green highly transparent films, but theones made using dyes of this invention had far superior light fastness:

The cyan dye D had the following structure

Chromaticity (Y) values were measured on a Minolta CM-3600dspectrophotometer using a C light source and 2° observer.

Exam- Dye (% Cyan D % T @ LF = ΔE/ ple w/w) (% w/w) Y x y 540 nm 100 hrs48  1 (2.3) 2.5 59.7 0.315 0.557 84 13.8 49  2 (2.5) 3.0 59.1 0.3110.560 83 16.9 50  9 (2.0) 2.5 59.1 0.306 0.550 83 15.1 51 17 (3.0) 2.055.0 0.287 0.578 80 13.3 52 23 (4.5) 1.5 55.2 0.301 0.571 78 14.0 53 26(2.9) 2.0 51.0 0.319 0.570 76 11.2 Comp.  E (4.5) 1.5 58.6 0.298 0.56083 42.3 4

Example 54

A photocurable ink was produced by mixing together NeoRad™ R441 (50parts; 33% solids UV-curable resin commercially available from AveciaLtd.), NeoCryl™ BT-175 (5 parts; 40% solids acrylic resin commerciallyavailable from Avecia Ltd.), 0.88 S.G. ammonia (2 parts), CGI 1700 (1part; photoinitiator commercially available from Ciba), azopyridone dyeof Example 3 (5 parts) and water (37 parts). The ink was applied to aglass substrate by bar-coating and exposed to UV-light through aphotomask. The unexposed portions of the film were then removed using a1% sodium carbonate solution at 25° C. and the remaining resin thermallycured at 150° C. for 30 minutes to produce a bright yellow patternedfilm.

Example 55

To an ink base comprising 90 parts water and 10 parts 2-pyrrolidone wasadded the dye of Example 2 to give a 4% solution of the dye in the inkbase. The solution was then adjusted to pH 10 using sodium hydroxide andfiltered through a 0.45μ membrane.

When this was applied to paper using an ink-jet printer, strong brightyellow prints were obtained with excellent fastness properties.

Further Inks for Colour Filters

Further inks which are suitable for making colour filters may beprepared having the formulations described in Tables I to VII belowwhere the numbers,denote parts by weight of each ingredient in theformulation. The compounds used may be in their free acid form and/or inthe form of any ffective salt. The number in the column headed compoundis an example number of a dye of the invention described herein with thenumber in brackets being the amount used (w/w). The followingabbreviations are also used in the tables:

DB199 = Direct Blue 199 DB86 = Direct Blue 86 DB87 = Direct Blue 87 AB9= Acid Blue 9 RB15 = Reactive Blue 15 CD = cyan D as given herein PAA =Poly(acrylic acid) of M_(W) 2000 X = Primid XL552 TEA = TriethanolamineTMP = Trimethylolpropane W= Water NMP = N-methyl-2-pyrrolidone 2P =2-pyrrolidone BE Butoxyethanol DEG = Diethylene glycol GBL =γ-butyrolactone ADBS = Ammonium dodecylbenzene sulphonate SDBS = Sodiumdodecylbenzene sulphonate SURF = Surfynol 465 (Non-ionic surfactantavailable from Air Products) AMP = 2-Amino-2-methyl-1-propanol AM =Ammonia (0.88 S.G.) HT = 4-Hydroxy-TEMPO; and HMBS =2-Hydroxy-4-methoxy-5-sulfobenzophenone.

TABLE I Com- DB- pound 199 DB86 PAA X W BE ADBS AMP AM 1(0.5)  3 15 5.560 1 15 2(0.25) 3. 12 4 69.25 5 0.5 6 12(1)    3 12 6 62 5 1 10 4(0.2) 2 4 1 88.8 1 3 5(0.5) 4 10 2 74.5 2 7 14(0.3)  3.5 12.5 4 61.4 5 0.812.5 7(1)   1.5 8 2 80.5 2 5 8(0.1)  2 0.9 11.5 6.5 63 5 11 6(3)    0.513.7 4.3 63.8 0.7 14 10(0.2)  2.8 15 5 61 1 15

TABLE II Com- DB- pound 199 PAA X TEA TMP W 2P ADBS AM 17(0.5) 4 14 561.5 1 14 22(0.5) 4 10.5 2.5 70 4 0.5 8 15(0.25) 3.5 15 5 60.5 0.75 1524(0.1) 2.9 12 3 67 5 10 13(2) 0.5 12 2 2 76 0.5 5 11(0.1) 0.9 8 5 81 14 16(0.1) 3 15 5 63 0.9 13

TABLE III Compound DB199 PAA TMP W 2P DEG GBL SURF SDBS AMP 18(0.5) 4 164 54.5 5 1 15   E(2.9) 0.1 12 3 71.2 0.8 10 19(3) 2 14 7 49 5 5 1520(0.1) 1 4 1 87.4 0.5 1.5 0.5 4 20(0.5) 1.5 8 3 80.5 2 0.5 4

TABLE IV Com- pound AB9 CD PAA X W DEG SURF AMP AM 19(3) 2 10 5 69 1 1025(3) 1.5 14.5 5 62.5 3 0.5 10 21(1) 4 18 7 50 5 15 22(3) 1 1 12 4 64.52 0.5 12  8(2.5) 2.5 15 7.5 56.5 1 15 18(1) 10 5 74.2 0.8 7 10(2) 2 103.5 67.5 5 10 11(2) 4 15 5 63.3 0.7 10

TABLE V Compound AB9 RB15 PAA X W BE GBL SURF SDBS AM 12(5) 2 13 4 55.25 0.8 15 13(3) 2 15 5 59 5 1 10 23(1) 2 8 4 74.5 2.5 2.5 0.5 5  6(0.5) 210 3 69.5 4 0.5 0.5 10 16(2) 2 15 7.5 52.5 1 20

TABLE VI Compound DB87 RB15 PAA X W HT HMSB ADBS AM 17(0.25)  3.5 13.5 463.5 1.75 0.5 14 18(0.1)  2.9 15 5 60 1 1 15 E(0.5)   3.5 0.5 12 6 65.512 1(0.25) 4.75 0.25 12 5 66.9 0.85 10 2(2) 0.5 12.5 4 68 1 12 3(1) 1.515 4.5 65.5 1 0.5 1 10 4(0.3) 3 12 4 67.8 0.9 12

TABLE VII Compound CD PAA X TEA W HT HMSB NMP BE ADBS AM 21(1) 3 15 553.5 2 5 0.5 15 21(2) 3 12 5 64 1 1 2 10  3(0.5) 4.5 12 2 2 64 2.5 2 20.5 8  4(0.2) 2.3 13 4.5 63.5 1.5 1 14

Further Inks for Ink Jet Printing

The inks described in Tables VII and IX may be prepared wherein thecompound described in the first column is the compound made in the aboveexample of the same number. Numbers quoted in the second column onwardsrefer to the number of parts of the relevant ingredient and all partsare by weight. The inks may be applied to paper by thermal or piezo inkjet printing.

The following abbreviations are used in Table I and II:

PG=propylene glycol

DEG=diethylene glycol

NMP=n-methyl pyrollidone

DMK=dimethylketone

IPA=isopropanol

MEOH=methanol

2P=2-pyrollidone

MIBK=methylisobutyl ketone

P12=propane-1,2-diol

BDL=butane-2,3-diol

CET=cetyl ammonium bromide

PHO=NA₂HPO4 and

TBT=tertiary butanol

TDG=thiodiglycol

What is claimed is:
 1. A compound of Formula (1)

in which: R¹ represents a group of Formula A:

where: c is from 2 to 6; R³ represents H or optionally substitutedC₁₋₈carbyl derived group; R⁴ and R⁵ independently represent an optionalsubstituent; R² represents an optionally substituted C₁₋₈carbyl derivedgroup; X, Y and Z independently represent H or an optional substituent;M represents H or a cation; and m and n independently represent 0, 1 or2.
 2. A compound of Formula (2):

in which: M represents H or a cation; Z is CONH₂, or CN; and R¹ isoptionally substituted C₂₋₈alkyl or a glycol group.
 3. A compositioncomprising an organic solvent free from water or water and one or morewater soluble organic solvent(s), and at least one compound of Formula(1):

in which: R¹ represents H, an optionally substituted C₁₋₈carbyl derivedgroup, or a group of Formula A:

where: c is from 2 to 6; R³ represents H or optionally substitutedC₁₋₈carbyl derived group; R⁴and R⁵ independently represent an optionalsubstituent; R² represents an optionally substituted C₁₋₈carbyl derivedgroup; X, Y and Z independently represent H or an optional substituent;M represents H or a cation; and m and n independently represent 0, 1 or2.
 4. A composition according to claim 3, which comprises at least onefurther colorant.
 5. A composition according to claim 4, where thefurther colorant is a cyan dye of Formula (3)

in which: T represents H or an optional substituent; V represents CO₂M,SO₃M, or PO₃M₂; M represents H or a cation; x and y independentlyrepresent 0 to 4; and x+y is from 3 to
 5. 6. A composition according toclaim 4, where the further colorant is selected from C.I. Pigment Green7 and C.I. Pigment Green
 36. 7. A process for preparing a patterned,cross-linked, polymer, film coating on a substrate comprising the stepsof (a) applying to the substrate simultaneously and/or sequentially inany order: (i) one or more cross linkable polymer precursor(s); (ii)optionally one or more additional cross-linker(s) capable ofcross-linking the precursor(s) for the polymer(s); and (iii) one or morecompound(s) of Formula (1) as described in claim 4 optionally with oneor more colorant(s); (b) optionally patterning one or more noncross-linked film(s) of component (i); component (ii); component (iii)and/or mixture(s) thereof, optionally before application of furthercomponents; and (c) initiating cross-linking the mixture of components(i), (ii) in situ, to form an optionally patterned, cross-linkedpolymeric film coating on the substrate.
 8. A process according to claim7, in which the process comprises a printing process.
 9. A processaccording to claim 8, in which the printing process is an ink-jetprinting process.
 10. A process according to claim 8, in which theprinting process comprises a photolithographic process.
 11. A processaccording to claim 9, in which the polymer precursor(s) comprise waterdissipatable polymer precursor(s).
 12. A substrate obtainable by aprocess as claimed in claim
 7. 13. A substrate according to claim 12,which comprises: a colour filter comprising a coloured, cross-linked,polymer coating on a transparent substrate; and/or a transparent,coloured, cross-linked, polymer coating on a substrate.
 14. A displaywhich comprises a substrate according to claim
 12. 15. A cartridgesuitable for use in an ink jet printer containing an ink according toclaim
 3. 16. A paper, overhead projector slide, textile or colour filterprinted with a composition according to claim
 3. 17. A colour filtercomprising red, green and blue filter elements, or yellow, magenta andcyan filter elements, wherein the filter carries a compound of Formula(1) as defined in claim 3.